Abstract:

A process for producing a blended fuel from a paraffin rich component and
a cyclic rich component, where each of the components are generated from
a renewable feedstock, is presented. The paraffin rich component is
generated from a first renewable feedstock comprising at least one
component selected from the group consisting of glycerides, free fatty
acids, biomass, lignocellulose, free sugars, and combinations thereof.
The cyclic rich component is generated from a second renewable feedstock
comprising at least one component selected from the group consisting of
glycerides, free fatty acids, free fatty alkyl esters, biomass,
lignocellulose, free sugars, and combinations thereof. The blended fuel
may a gasoline boiling point range blended fuel, a diesel boiling point
range blended fuel, an aviation boiling point range blended fuel, any
combination thereof, or any mixture thereof.

Claims:

1. A process of producing a blended fuel from renewable feedstocks
comprising:a) generating at least one paraffin rich component from a
first renewable feedstock comprising at least one component selected from
the group consisting of glycerides, free fatty acids, biomass,
lignocellulose, free sugars, and combinations thereof;b) generating at
least one cyclic rich component from a second renewable feedstock
comprising at least one component selected from the group consisting of
glycerides, free fatty acids, biomass, lignocellulose, free sugars, and
combinations thereof; andc) blending at least a portion of the paraffin
rich component and at least a portion of the cyclic rich component to
form at least one blended fuel selected from the group consisting of a
gasoline boiling point range blended fuel, a diesel boiling point range
blended fuel, an aviation boiling point range blended fuel, any
combination thereof, and any mixture thereof.

2. The process of claim 1 wherein the generating of at least one paraffin
rich component from a first renewable feedstock comprises deoxygenation
and isomerization.

3. The process of claim 1 wherein the generating of at least one paraffin
rich component from a first renewable feedstock comprises gasification
followed by oligomerization.

4. The process of claim 1 wherein the generating of at least one paraffin
rich component from a first renewable feedstock comprises deoxygenation,
isomerization, and hydrocracking.

5. The process of claim 1 wherein the generating of at least one paraffin
rich component from a first renewable feedstock comprises oligomerization
and deoxygenation.

6. The process of claim 1 wherein the generating of at least one paraffin
rich component from a second renewable feedstock comprises gasification
to synthesis gas, synthesis gas conversion to light oxygenates, light
oxygenates conversion to paraffins, dehydration to olefins, and olefin
oligomerization.

7. The process of claim 1 wherein the generating of at least one paraffin
rich component from a second renewable feedstock comprises gasification
to synthesis gas, synthesis gas conversion to light oxygenates, light
oxygenates conversion to paraffins followed by methanol to gasoline.

8. The process of claim 1 wherein the generating of at least one paraffin
rich component from a second renewable feedstock comprises fermentation,
dehydrogenation of light oxygenates to olefins, and oligomerization.

9. The process of claim 1 wherein the generating of at least one paraffin
rich component from a second renewable feedstock comprises fermentation,
conversion of light oxygenates to paraffins.

10. The process of claim 1 wherein the generating of at least one cyclic
rich component from a second renewable feedstock comprises deoxygenation,
isomerization, and cyclization.

11. The process of claim 1 wherein the generating of at least one cyclic
rich component from a second renewable feedstock comprises gasification
followed by oligomerization and cyclization.

12. The process of claim 1 wherein the generating of at least one cyclic
rich component from a second renewable feedstock comprises deoxygenation,
isomerization, hydrocracking and cyclization.

13. The process of claim 1 wherein the generating of at least one cyclic
rich component from a second renewable feedstock comprises
oligomerization, deoxygenation and cyclization.

14. The process of claim 1 wherein the generating of at least one cyclic
rich component from a second renewable feedstock comprises deoxygenation,
cyclization, and aromatization.

15. The process of claim 1 wherein the generating of at least one cyclic
rich component from a second renewable feedstock comprises gasification
followed by oligomerization and cyclization, and aromatization.

16. The process of claim 1 wherein the generating of at least one cyclic
rich component from a second renewable feedstock comprises deoxygenation,
hydrocracking, cyclization, and aromatization.

17. The process of claim 1 wherein the generating of at least one cyclic
rich component from a second renewable feedstock comprises deoxygenation,
isomerization, and hydrocracking, cyclization, and aromatization.

18. The process of claim 1 wherein the generating of at least one cyclic
rich component from a second renewable feedstock comprises pyrolysis and
deoxygenation.

19. The process of claim 1 wherein the generating of at least one cyclic
rich component from a second renewable feedstock comprises liquefaction
followed by hydrodeoxygenation.

20. The process of claim 1 wherein the generating of at least one cyclic
rich component from a second renewable feedstock comprises gasification
to produce synthesis gas, synthesis gas conversion to light oxygenates,
light oxygenates conversion to paraffins, paraffin dehydrogenation to
olefin, followed by olefin cyclooligomerization.

21. The process of claim 1 wherein the generating of at least one cyclic
rich component from a second renewable feedstock comprises gasification
to produce synthesis gas, synthesis gas conversion to light oxygenates,
and light oxygenates conversion to a mixed hydrocarbon stream comprising
cycloparaffins and aromatics.

22. The process of claim 1 wherein the generating of at least one cyclic
rich component from a second renewable feedstock comprises fermentation
to light oxygenates, dehydration of oxygenates to olefins, and olefin
cyclooligomerization.

23. The process of claim 1 wherein the generating of at least one cyclic
rich component from a second renewable feedstock comprises fermentation
to light oxygenates, and light oxygenates conversion to a mixed
hydrocarbon stream comprising cycloparaffins and aromatics.

24. The process of claim 1 wherein the first renewable feedstock and the
second renewable are the same.

25. The process of claim 1 wherein the first renewable feedstock and the
second renewable feedstock are at least partially derived from the same
renewable source.

26. The process of claim 1 wherein the blended fuel comprises a mixture of
at least two of gasoline boiling point range blended fuel, diesel boiling
point range blended fuel, an aviation boiling point range blended fuel,
said process further comprising fractionating the blended fuel to form at
least a first and a second fractionated blended fuel selected from the
group consisting of gasoline boiling point range fuel, diesel boiling
point range fuel, and aviation boiling point range fuel.

27. The process of claim 1 further comprising separating the paraffin rich
component into a gasoline boiling point range paraffin rich component, a
diesel boiling point range paraffin rich component, and an aviation
boiling point range paraffin rich component and separating the cyclic
rich component into a gasoline boiling point range cyclic rich component,
a diesel boiling point range cyclic rich component, and an aviation
boiling point range cyclic rich component.

28. The process of claim 1 wherein at least one of the renewable
feedstocks is in a mixture or co-feed with a petroleum hydrocarbon
feedstock.

29. A diesel boiling point range blended fuel, an aviation boiling point
range blended fuel, and a gasoline boiling point range blended fuel as
produced by the process of claim 1.

30. The process of claim 1 further comprising mixing one or more additives
to at least one of the diesel boiling point range blended fuel, the
aviation boiling point range blended fuel, and the gasoline boiling point
range blended fuel.

31. A blended fuel meeting the specification of MTL-DTL-83133 wherein at
least one component of the blended fuel is the aviation boiling point
range blended fuel produced by the process of claim 1.

32. A blended fuel comprising the gasoline boiling point range blended
fuel of claim 1 and a component produced from processing a petroleum
feedstock.

33. A blended fuel comprising the aviation boiling point range blended
fuel of claim 1 and a component produced from processing a petroleum
feedstock.

34. A blended fuel comprising the diesel boiling point range blended fuel
of claim 1 and a component produced from processing a petroleum
feedstock.

Description:

CROSS-REFERENCE TO RELATED APPLICATION

[0001]This application claims priority from Provisional Application Ser.
No. 61/042,739 filed Apr. 6, 2008, the contents of which are hereby
incorporated by reference in its entirety.

BACKGROUND OF THE INVENTION

[0003]The process produces one or more blended fuels from renewable
feedstocks including glycerides, free fatty acids, biomass,
lignocellulose, free sugars, and combinations thereof. At least one
paraffin rich component is produced from at least one of the renewable
feedstocks and at least one cyclic rich component is produced from a
renewable feedstock. At least one paraffin rich fuel component and at
least one cyclic rich fuel component are blended to form at least one
fuel.

[0004]In one exemplary embodiment, the generation of the paraffin rich
component employs a process for producing hydrocarbons useful as at least
diesel fuel and aviation fuel or fuel blending components from renewable
feedstocks such as the triglycerides and free fatty acids found in
materials such as plant oils, fish oils, animal fats, and greases. The
process involves hydrogenation, deoxygenation (decarboxylation,
decarbonylation, and/or hydrodeoxygenation) in at least a first zone and
hydroisomerization and hydrocracking in at least a second zone. A
selective hot high pressure hydrogen stripper is used to remove at least
the carbon oxides from the hydrogenation, decarboxylation and/or
hydrodeoxygenation zone effluent before entering the hydroisomerization
and hydrocracking zone. Optionally, a diesel range stream, a
naphtha/gasoline range stream, a naphtha/gasoline and LPG range stream,
or any mixture thereof is used as an additional rectification agent in
the selective hot high pressure hydrogen stripper to decrease the amount
of product carried in the overhead thereby reducing the amount of
n-paraffins in the diesel and aviation fuels.

[0005]As the demand for gasoline, diesel fuel, and aviation fuel increases
worldwide there is increasing interest in sources other than petroleum
crude oil for producing these fuels. One such source is what has been
termed renewable feedstocks. These renewable feedstocks include, but are
not limited to, plant oils such as jatropha, camelina, crambe, corn,
rapeseed, canola, soybean and algal oils, animal fats such as tallow,
fish oils and various waste streams such as yellow and brown greases and
sewage sludge. The common feature of these feedstocks is that they are
composed of glycerides and Free Fatty Acids (FFA). Both of these
compounds contain aliphatic carbon chains having from about 8 to about 24
carbon atoms. The aliphatic carbon chains in the glycerides or FFAs can
also be mono-, di- or poly-unsaturated. Some of the glycerides from the
renewable sources may be monoglycerides or diglycerides instead of or in
addition to the trigylcerides. Fatty acid alkyl esters may be the
feedstock or present in the feedstock. Examples include fatty acid methyl
ester and fatty acid ethyl ester.

[0006]There are reports in the art disclosing the production of
hydrocarbons from oils. For example, U.S. Pat. No. 4,300,009 discloses
the use of crystalline aluminosilicate zeolites to convert plant oils
such as corn oil to hydrocarbons such as gasoline and chemicals such as
paraxylene. U.S. Pat. No. 4,992,605 discloses the production of
hydrocarbon products in the diesel boiling point range by hydroprocessing
vegetable oils such as canola or sunflower oil. Finally, US 2004/0230085
A1 discloses a process for treating a hydrocarbon component of biological
origin by hydrodeoxygenation followed by isomerization.

[0007]The paraffin rich blending component is generated by a process which
comprises one or more steps to hydrogenate, deoxygenate, isomerize and
selectively hydrocrack a renewable feedstock in order to generate a
gasoline range product, a diesel range product, and an aviation range
product. Simply hydrogenating and deoxygenating the renewable feedstock
in a hydrogen environment in the presence of a hydrotreating catalyst
results in straight chain paraffins having chain-lengths similar to, or
slightly shorter than, the fatty acid composition of the feedstock. With
many feedstocks, this approach results in a fuel meeting the general
parameters for a diesel fuel, but not those for an aviation fuel. The
selective hydrocracking reaction reduces the carbon chain length to allow
selectivity to aviation fuel range paraffins while minimizing lower
molecular weight products. The volume ratio of recycle hydrocarbon to
feedstock ranges from about 0.1:1 to about 8:1 and provides a mechanism
to limit reaction zone temperature rise, increase the hydrogen
solubility, and more uniformly distribute the heat of reaction in the
reaction mixture. As a result of the recycle, some embodiments may use
less processing equipment, less excess hydrogen, less utilities, or any
combination of the above.

[0008]The performance of the isomerization and selective hydrocracking
catalyst is improved by removing at least carbon dioxide from the feed to
the isomerization and selective hydrocracking zone. The presence of
oxygen containing molecules including water, carbon dioxide, and other
carbon oxides may result in the deactivation of the isomerization
catalyst. The oxygen containing molecules such as carbon dioxide, carbon
monoxide and water are removed using a selective hot high pressure
hydrogen stripper which optionally contains a rectification zone.

[0009]In one exemplary embodiment, the generation of the cyclic rich
component employs a process for obtaining cyclic rich component from
biomass. More particularly, this process relates to the treatment of
cellulosic waste, or pyrolysis oil, produced from the pyrolysis of
biomass to produce fuel or fuel blending or additive components. The
fuel, fuel additives, or blending components may include those in the
gasoline boiling point range, the diesel boiling point range, and the
aviation boiling point range.

[0010]As discussed above, renewable energy sources are of increasing
importance. They are a means of reducing dependence on petroleum oil and
provide a substitute for fossil fuels. Also, renewable resources can
provide for basic chemical constituents to be used in other industries,
such as chemical monomers for the making of plastics. Biomass is a
renewable resource that can provide some of the needs for sources of
chemicals and fuels.

[0011]Biomass includes, but is not limited to, lignin, plant parts,
fruits, vegetables, plant processing waste, wood chips, chaff, grain,
grasses, corn, corn husks, weeds, aquatic plants, hay, paper, paper
products, recycled paper and paper products, and any cellulose containing
biological material or material of biological origin. Lignocellulosic
biomass, or cellulosic biomass as used throughout the remainder of this
document, consists of the three principle biopolymers cellulose,
hemicellulose, and lignin. The ratio of these three components varies
depending on the biomass source. Cellulosic biomass might also contain
lipids, ash, and protein in varying amounts. The economics for converting
biomass to fuels or chemicals depend on the ability to produce large
amounts of biomass on marginal land, or in a water environment where
there are few or no other significantly competing economic uses of that
land or water environment. The economics can also depend on the disposal
of biomass that would normally be placed in a landfill.

[0012]The growing, harvesting and processing of biomass in a water
environment provides a space where there is plenty of sunlight and
nutrients while not detracting from more productive alternate uses.
Biomass is also generated in many everyday processes as a waste product,
such as waste material from crops. In addition, biomass contributes to
the removal of carbon dioxide from the atmosphere as the biomass grows.
The use of biomass can be one process for recycling atmospheric carbon
while producing fuels and chemical precursors. Biomass when heated at
short contact times in an environment with low or no oxygen, termed
pyrolysis, will generate a liquid product known as pyrolysis oil.
Synonyms for pyrolysis oil include bio-oil, pyrolysis liquids, bio-crude
oil, wood liquids, wood oil, liquid smoke, wood distillates, pyroligneous
acid, and liquid wood.

[0013]The product of the biomass pyrolysis, the pyrolysis oil, contains
what is known as pyrolytic lignin. Pyrolytic lignin is the water
insoluble portion of the pyrolysis oil. The pyrolysis oil may be
processed whole, or a portion of the aqueous phase may be removed to
provide a pyrolysis oil enriched in pyrolytic lignin which is processed
through deoxygenation to produce the cyclic rich fuel blending component.

[0014]At least one paraffin rich component and at least one cyclic rich
component are blended to form a fuel. The blending is controlled so that
the blended fuel meets specific requirements of a target fuel. Other
additives or components may be blended with the paraffin rich component
and the cyclic rich component in order to meet additional requirements of
the target fuel. The target fuel may be in the boiling point ranges of
gasoline, aviation, and diesel, and may be entirely derived from
renewable sources. The target fuel is designed to power engines or
devices that are currently distributed around the world without requiring
upgrades to those engines. The target fuel may be blended to meet the
specifications using entirely renewable feedstock derived blending
components.

SUMMARY OF THE INVENTION

[0015]A process of producing a blended fuel from renewable feedstocks
comprises generating at least one paraffin rich component from a first
renewable feedstock of at least one of glycerides, free fatty acids,
biomass, lignocellulose, free sugars, and combinations thereof,
generating a cyclic rich component from a second renewable feedstock of
at least one of glycerides, free fatty acids, biomass, lignocellulose,
free sugars, and combinations thereof, and blending at least a portion of
the paraffin rich component and at least a portion of the cyclic rich
component to form at least one blended fuel. The blended fuel may be a
mixture of at least two of a gasoline boiling point range blended fuel, a
diesel boiling point range blended fuel, an aviation boiling point range
blended fuel, or the blended fuel may be at least one of a gasoline
boiling point range blended fuel, a diesel boiling point range blended
fuel, an aviation boiling point range blended fuel.

BRIEF DESCRIPTION OF THE DRAWINGS

[0016]FIG. 1 is a schematic of one embodiment a process for generating the
paraffin rich component. FIG. 1 shows the option where a portion of the
branched-paraffin-enriched product is conducted to the hot high pressure
hydrogen stripper as a rectification agent to decrease the amount of
first reaction zone product carried in the overhead of the selective hot
high pressure hydrogen stripper. Other hydrocarbon streams may be used as
a rectification agent.

[0017]FIG. 2 is a schematic of one embodiment of a process for generating
the cyclic rich component. FIG. 2 shows the option where the whole
pyrolysis oil is processed through two stages of deoxygenation.

[0018]FIG. 3 is a plot of the boiling point distribution of several fully
deoxygenated pyrolysis oils suitable as the cyclic component which shows
the hydrocarbon products produced have a wide boiling point range with
significant fractions in the range for each fuel.

DETAILED DESCRIPTION OF THE INVENTION

[0019]The invention provides a process for generating at least one
paraffin rich component from a renewable feedstock and at least one
cyclic rich component from a renewable feedstock, and blending at least
those two components to provide a blended fuel.

Generating the Paraffin Rich Component

[0020]The paraffin rich component may be one or more hydrocarbon streams,
a diesel boiling point range product, an aviation boiling point range
product, and a naphtha/gasoline boiling point range product from
renewable feedstocks such as feedstocks originating from plants or
animals. The term "rich" is meant to indicate at least 40 mass-%. The
term renewable feedstock is meant to include feedstocks other than those
obtained from petroleum crude oil. Suitable feedstocks include any of
glycerides, free fatty acids, biomass, lignocellulose (including lignin,
cellulose, and hemicellulose), free sugars, and combinations thereof.

[0021]There are multiple different routes to the generation of a paraffin
rich component from the renewable feedstock. One includes deoxygenation
and isomerization as described in detail below, and described in U.S.
Application No. 60/973,797; U.S. Application No. 60/973,788; U.S.
Application No. 60/093,792; U.S. Application No. 60/973,816; U.S.
Application No. 60/973,795; U.S. Application No. 60/973,800; and U.S.
Application No. 60/973,818.

[0022]Another route to generating at least one paraffin rich component
from a renewable feedstock is deoxygenation, isomerization, and
hydrocracking, See U.S. Application Nos. 61/037,066 and 61/037,124.

[0025]Further routes involves the generation of synthesis gas from biomass
by gasification, conversion of the synthesis gas to light oxygenates such
as alcohols, and conversion of the light alcohols to paraffins and/or
olefins, and optional oligomerization.

[0026]The biomass undergo fermentation to generate light oxygenates which
are then converted to paraffins. The light oxygenates may be dehydrated
to form olefins which are then oligomerized.

[0027]The following description is a detailed example of one route to
generating the paraffin rich component from a renewable feedstock. In
this example, the renewable feedstock that can be used to generate the
paraffin rich component include any of those which comprise glycerides
and free fatty acids (FFA) and or free fatty alkyl esters. Most of the
glycerides will be triglycerides, but monoglycerides and diglycerides may
be present and processed as well. Examples of these renewable feedstocks
include, but are not limited to, canola oil, corn oil, soy oils, rapeseed
oil, soybean oil, colza oil, tall oil, sunflower oil, hempseed oil, olive
oil, linseed oil, coconut oil, castor oil, peanut oil, palm oil, mustard
oil, cottonseed oil, tallow, yellow and brown greases, lard, train oil,
fats in milk, fish oil, algal oil, sewage sludge, cuphea oil, camelina
oil, jatropha oil, crambe oil, curcas oil, babassu oil, palm kernel oil,
and the like. The glycerides and FFAs and or fatty acid alkyl esters of
the typical vegetable or animal fat contain aliphatic hydrocarbon chains
in their structure which have about 8 to about 24 carbon atoms with a
majority of the fats and oils containing high concentrations of fatty
acids with 16 and 18 carbon atoms. Mixtures or co-feeds of renewable
feedstocks and fossil fuel derived hydrocarbons, such as
petroleum-derived hydrocarbons, may also be used as the feedstock. Other
feedstock components which may be used, especially as a co-feed component
in combination with the above listed feedstocks include spent motor oils
and industrial lubricants, used paraffin waxes, liquids derived from the
gasification of coal, biomass, natural gas followed by a downstream
liquefaction step such as Fischer-Tropsch technology, liquids derived
from depolymerization, thermal or chemical, of waste plastics such as
polypropylene, high density polyethylene, and low density polyethylene;
and other synthetic oils generated as byproducts from petrochemical and
chemical processes. Mixtures of the above feedstocks may also be used as
co-feed components. One advantage of using a co-feed component is the
transformation of what has been considered to be a waste product from a
petroleum based or other process into a valuable co-feed component to the
current process.

[0028]The renewable feedstocks that can be used to generate the paraffin
rich component may contain a variety of impurities. For example, tall oil
is a byproduct of the wood processing industry and tall oil contains
esters and rosin acids in addition to FFAs. Rosin acids are cyclic
carboxylic acids. The renewable feedstocks may also contain contaminants
such as alkali metals, e.g. sodium and potassium, phosphorous as well as
solids, water and detergents. An optional first step is to remove as much
of these contaminants as possible. One possible pretreatment step
involves contacting the renewable feedstock with an ion-exchange resin in
a pretreatment zone at pretreatment conditions. The ion-exchange resin is
an acidic ion exchange resin such as Amberlyst®-15 and can be used as
a bed in a reactor through which the feedstock is flowed through, either
upflow or downflow.

[0029]Another possible means for removing contaminants is a mild acid
wash. This is carried out by contacting the feedstock with an acid such
as sulfuric, nitric, phosphoric, or hydrochloric and water in a reactor.
The acidic aqueous solution and feedstock can be contacted either in a
batch or continuous process. Contacting is done with a dilute acid
solution usually at ambient temperature and atmospheric pressure. If the
contacting is done in a continuous manner, it is usually done in a
counter current manner. Yet another possible means of removing metal
contaminants from the feedstock is through the use of guard beds which
are well known in the art. These can include alumina guard beds either
with or without demetallation catalysts such as nickel or cobalt.
Filtration and solvent extraction techniques are other choices which may
be employed. Hydroprocessing such as that described in U.S. application
Ser. No. 11/770,826, hereby incorporated by reference, is another
pretreatment technique which may be employed.

[0030]The renewable feedstock is flowed to a first reaction zone
comprising one or more catalyst beds in one or more reactors. The term
"feedstock" is meant to include feedstocks that have not been treated to
remove contaminants as well as those feedstocks purified in a
pretreatment zone. In the reaction first zone, the feedstock is contacted
with a hydrogenation or hydrotreating catalyst in the presence of
hydrogen at hydrogenation conditions to hydrogenate the reactive
components such as olefinic or unsaturated portions of the fatty acid
chains. Hydrogenation and hydrotreating catalysts are any of those well
known in the art such as nickel or nickel/molybdenum dispersed on a high
surface area support. Other hydrogenation catalysts include one or more
noble metal catalytic elements dispersed on a high surface area support.
Non-limiting examples of noble metals include Pt and/or Pd dispersed on
gamma-alumina or activated carbon. Hydrogenation conditions include a
temperature of about 40° C. to about 400° C. and a pressure
of about 689 kPa absolute (100 psia) to about 13,790 kPa absolute (2000
psia). In another embodiment the hydrogenation conditions include a
temperature of about 200° C. to about 300° C. and a
pressure of about 1379 kPa absolute (200 psia) to about 4826 kPa absolute
(700 psia). Other operating conditions for the hydrogenation zone are
well known in the art.

[0031]The catalysts enumerated above are also capable of catalyzing
decarboxylation, decarbonylation and/or hydrodeoxygenation of the
feedstock to remove oxygen. Decarboxylation, decarbonylation, and
hydrodeoxygenation are herein collectively referred to as deoxygenation
reactions. Decarboxylation conditions include a relatively low pressure
of about 689 kPa (100 psia) to about 6895 kPa (1000 psia), a temperature
of about 200° C. to about 400° C. and a liquid hourly space
velocity of about 0.5 to about 10 hr-1. In another embodiment the
decarboxylation conditions include the same relatively low pressure of
about 689 kPa (100 psia) to about 6895 kPa (1000 psia), a temperature of
about 288° C. to about 345° C. and a liquid hourly space
velocity of about 1 to about 4 hr-1. Since hydrogenation is an
exothermic reaction, as the feedstock flows through the catalyst bed the
temperature increases and decarboxylation and hydrodeoxygenation will
begin to occur. Thus, it is envisioned and is within the scope of this
invention that all the reactions occur simultaneously in one reactor or
in one bed. Alternatively, the conditions can be controlled such that
hydrogenation primarily occurs in one bed and decarboxylation and/or
hydrodeoxygenation occurs in a second bed. Of course if only one bed is
used, then hydrogenation occurs primarily at the front of the bed, while
decarboxylation/hydrodeoxygenation occurs mainly in the middle and bottom
of the bed. Finally, desired hydrogenation can be carried out in one
reactor, while decarboxylation, decarbonylation, and/or
hydrodeoxygenation can be carried out in a separate reactor.

[0032]The reaction product from the hydrogenation and deoxygenation
reactions will comprise both a liquid portion and a gaseous portion. The
liquid portion comprises a hydrocarbon fraction comprising n-paraffins
and having a large concentration of paraffins in the 15 to 18 carbon
number range. Different feedstocks will result in different distributions
of paraffins. A portion of this hydrocarbon fraction, after separation
from the gaseous portion, may be used as the hydrocarbon recycle
described above. Although this hydrocarbon fraction is useful as a diesel
fuel or diesel fuel blending component, additional fuels, such as
aviation fuels or aviation fuel blending components which typically have
a concentration of paraffins in the range of about 9 to about 15 carbon
atoms, may be produced with additional processing. Also, because the
hydrocarbon fraction comprises essentially all n-paraffins, it will have
poor cold flow properties. Many diesel and aviation fuels and blending
components must have better cold flow properties and so the reaction
product is further reacted under isomerization conditions to isomerize at
least a portion of the n-paraffins to branched paraffins.

[0033]The gaseous portion comprises hydrogen, carbon dioxide, carbon
monoxide, water vapor, propane and perhaps sulfur components such as
hydrogen sulfide or phosphorous component such as phosphine. The effluent
from the deoxygenation zone is conducted to a hot high pressure hydrogen
stripper. One purpose of the hot high pressure hydrogen stripper is to
selectively separate at least a portion of the gaseous portion of the
effluent from the liquid portion of the effluent. As hydrogen is an
expensive resource, to conserve costs, the separated hydrogen is recycled
to the first reaction zone containing the deoxygenation reactor. Also,
failure to remove the water, carbon monoxide, and carbon dioxide from the
effluent may result in poor catalyst performance in the isomerization
zone. Water, carbon monoxide, carbon dioxide, any ammonia or hydrogen
sulfide are selectively stripped in the hot high pressure hydrogen
stripper using hydrogen. The hydrogen used for the stripping may be dry,
and free of carbon oxides. The temperature may be controlled in a limited
range to achieve the desired separation and the pressure may be
maintained at approximately the same pressure as the two reaction zones
to minimize both investment and operating costs. The hot high pressure
hydrogen stripper may be operated at conditions ranging from a pressure
of about 689 kPa absolute (100 psia) to about 13,790 kPa absolute (2000
psia), and a temperature of about 40° C. to about 350° C.
In another embodiment the hot high pressure hydrogen stripper may be
operated at conditions ranging from a pressure of about 1379 kPa absolute
(200 psia) to about 4826 kPa absolute (700 psia), or about 2413 kPa
absolute (350 psia) to about 4882 kPa absolute (650 psia), and a
temperature of about 50° C. to about 350° C. The hot high
pressure hydrogen stripper may be operated at essentially the same
pressure as the reaction zone. By "essentially", it is meant that the
operating pressure of the hot high pressure hydrogen stripper is within
about 1034 kPa absolute (150 psia) of the operating pressure of the
reaction zone. For example, in one embodiment the hot high pressure
hydrogen stripper separation zone is no more than 1034 kPa absolute (150
psia) less than that of the reaction zone.

[0034]The effluent enters the hot high pressure stripper and at least a
portion of the gaseous components, are carried with the hydrogen
stripping gas and separated into an overhead stream. The remainder of the
deoxygenation zone effluent stream is removed as hot high pressure
hydrogen stripper bottoms and contains the liquid hydrocarbon fraction
having components such as normal hydrocarbons having from about 8 to 24
carbon atoms. A portion of this liquid hydrocarbon fraction in hot high
pressure hydrogen stripper bottoms may be used as the hydrocarbon recycle
described below.

[0035]A portion of the lighter hydrocarbons generated in the deoxygenation
zone may be also carried with the hydrogen in the hot high pressure
hydrogen stripper and removed in the overhead stream. Any hydrocarbons
removed in the overhead stream will effectively bypass the isomerization
zone, discussed below. A large portion of the hydrocarbons bypassing the
isomerization zone will be normal hydrocarbons which, due to bypassing
the isomerization stage, will not be isomerized to branched hydrocarbons.
At least a portion of these normal hydrocarbons ultimately end up in the
diesel range product or the aviation range product, and depending upon
the specifications required for the products, the normal hydrocarbons may
have an undesired effect on the diesel range product and the aviation
range product. For example, in applications where the diesel range
product is required to meet specific cloud point specifications, or where
the aviation range product is required to meet specific freeze point
specifications, the normal hydrocarbons from the hot high pressure
hydrogen stripper overhead may interfere with meeting the required
specification. Therefore, in some applications it is advantageous to take
steps to prevent normal hydrocarbons from being removed in the hot high
pressure hydrogen stripper overhead and bypassing the isomerization zone.
For example, one or more, or a mixture of additional rectification agents
may be optionally introduced into the hot high pressure hydrogen stripper
to reduce the amount of hydrocarbons in the hot high pressure hydrogen
stripper overhead stream. Suitable example of additional rectification
agents include the diesel boiling point range product, the aviation
boiling point range product, the naphtha/gasoline boiling range product,
the mixture of naphtha/gasoline and LPG, or any combinations thereof.
These streams may be recycled and introduced to the hot high pressure
hydrogen stripper, at a location of the stripper that is above the
deoxygenation zone effluent introduction location and in the
rectification zone. The rectification zone, if present, may contain vapor
liquid contacting devices such as trays or packing to increase the
efficiency of the rectification. The optional rectification agent would
operate to force an increased amount of the hydrocarbon product from the
deoxygenation zone to travel downward in the hot high pressure hydrogen
stripper and be removed in the hot high pressure hydrogen stripper
bottoms stream instead of being carried with the stripping hydrogen gas
into the hot high pressure hydrogen stripper overhead. Other
rectification agents from independent sources may be used instead of, or
in combination with, the diesel boiling point range product, the
naphtha/gasoline product, and the naphtha/gasoline and LPG stream.

[0036]Hydrogen is a reactant in at least some of the reactions above, and
a sufficient quantity of hydrogen must be in solution to most effectively
take part in the catalytic reaction. Past processes have operated at high
pressures in order to achieve a desired amount of hydrogen in solution
and readily available for reaction. However, higher pressure operations
are more costly to build and to operate as compared to their lower
pressure counterparts. One advantage of the present invention is the
operating pressure may be in the range of about 1379 kPa absolute (200
psia) to about 4826 kPa absolute (700 psia) which is lower than that
found in other previous operations. In another embodiment the operating
pressure is in the range of about 2413 kPa absolute (350 psia) to about
4481 kPa absolute (650 psia), and in yet another embodiment operating
pressure is in the range of about 2758 kPa absolute (400 psia) to about
4137 kPa absolute (600 psia). Furthermore, the rate of reaction is
increased resulting in a greater amount of throughput of material through
the reactor in a given period of time.

[0037]In one embodiment, the desired amount of hydrogen is kept in
solution at lower pressures by employing a large recycle of hydrocarbon
to the deoxygenation reaction zone. Other processes have employed
hydrocarbon recycle in order to control the temperature in the reaction
zones since the reactions are exothermic reactions. However, the range of
recycle to feedstock ratios used herein is determined not on temperature
control requirements, but instead, based upon hydrogen solubility
requirements. Hydrogen has a greater solubility in the hydrocarbon
product than it does in the feedstock. By utilizing a large hydrocarbon
recycle the solubility of hydrogen in the combined liquid phase in the
reaction zone is greatly increased and higher pressures are not needed to
increase the amount of hydrogen in solution. In one embodiment of the
invention, the volume ratio of hydrocarbon recycle to feedstock is from
about 2:1 to about 8:1. In another embodiment the ratio is in the range
of about 3:1 to about 6:1 and in yet another embodiment the ratio is in
the range of about 4:1 to about 5:1.

[0038]Although the hydrocarbon fraction separated in the hot high pressure
hydrogen stripper is useful as a diesel fuel or diesel fuel blending
component, because it comprises essentially n-paraffins, it will have
poor cold flow properties. Also, depending upon the feedstock, the amount
of hydrocarbons suitable for aviation fuel or aviation fuel blending
component may be small. Therefore the hydrocarbon fraction is contacted
with an isomerization catalyst under isomerization conditions to at least
partially isomerize the n-paraffins to branched paraffins and improve the
cold flow properties of the liquid hydrocarbon fraction. The
isomerization catalysts and operating conditions are selected so that the
isomerization catalyst also catalyzes selective hydrocracking of the
paraffins. The selective hydrocracking creates hydrocarbons in the
aviation boiling point range. The effluent of the second reaction zone,
the isomerization and selective hydrocracking zone, is a
branched-paraffin-enriched stream. By the term "enriched" it is meant
that the effluent stream has a greater concentration of branched
paraffins than the stream entering the isomerization zone, and preferably
comprises greater than 50 mass-% branched paraffms. It is envisioned that
the isomerization zone effluent may contains 70, 80, or 90 mass-%
branched paraffins. Isomerization and selective hydrocracking can be
carried out in a separate bed of the same reactor, described above or the
isomerization and selective hydrocracking can be carried out in a
separate reactor. For ease of description, the following will address the
embodiment where a second reactor is employed for the isomerization and
selective hydrocracking reactions. The hydrogen stripped product of the
deoxygenation reaction zone is contacted with an isomerization and
selective hydrocracking catalyst in the presence of hydrogen at
isomerization and selective hydrocracking conditions to isomerize at
least a portion of the normal paraffins to branched paraffins. Due to the
presence of hydrogen, the reactions may be called hydroisomerization and
hydrocracking.

[0039]The isomerization and selective hydrocracking of the paraffinic
product can be accomplished in any manner known in the art or by using
any suitable catalyst known in the art. One or more beds of catalyst may
be used. It is preferred that the isomerization be operated in a
co-current mode of operation. Fixed bed, trickle bed down flow or fixed
bed liquid filled up-flow modes are both suitable. See also, for example,
US 2004/0230085 A1 which is incorporated by reference in its entirety.
Catalysts having an acid function and mild hydrogenation function are
favorable for catalyzing both the isomerization reaction and the
selective hydrocracking reaction. Suitable catalysts comprise a metal of
Group VIII (IUPAC 8-10) of the Periodic Table and a support material.
Suitable Group VIII metals include platinum and palladium, each of which
may be used alone or in combination. The support material may be
amorphous or crystalline or a combination of the two. Suitable support
materials include aluminas, amorphous silica-aluminas, ferrierite,
ALPO-31, SAPO-11, SAPO-31, SAPO-37, SAPO-41, SM-3, MgAPSO-31, FU-9,
NU-10, NU-23, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57,
MeAPO-11, MeAPO-31, MeAPO-41, MeAPSO-11, MeAPSO-31, MeAPSO-41, MeAPSO-46,
ELAPO-11, ELAPO-31, ELAPO-41, ELAPSO-11, ELAPSO-31, ELAPSO-41,
laumontite, cancrinite, offretite, hydrogen form of stillbite, magnesium
or calcium form of mordenite, and magnesium or calcium form of partheite,
each of which may be used alone or in combination. ALPO-31 is described
in U.S. Pat. No. 4,310,440. SAPO-11, SAPO-31, SAPO-37, and SAPO-41 are
described in U.S. Pat. No. 4,440,871. SM-3 is described in U.S. Pat. No.
4,943,424; U.S. Pat. No. 5,087,347; U.S. Pat. No. 5,158,665; and U.S.
Pat. No. 5,208,005. MgAPSO is a MeAPSO, which is an acronym for a metal
aluminumsilicophosphate molecular sieve, where the metal Me is magnesium
(Mg). Suitable MeAPSO-31 catalysts include MgAPSO-31. MeAPSOs are
described in U.S. Pat. No. 4,793,984, and MgAPSOs are described in U.S.
Pat. No. 4,758,419. MgAPSO-31 is a preferred MgAPSO, where 31 means a
MgAPSO having structure type 31. Many natural zeolites, such as
ferrierite, that have an initially reduced pore size can be converted to
forms suitable for selective hydrocracking and isomerization by removing
associated alkali metal or alkaline earth metal by ammonium ion exchange
and calcination to produce the substantially hydrogen form, as taught in
U.S. Pat. No. 4,795,623 and U.S. Pat. No. 4,924,027. Further catalysts
and conditions for skeletal isomerization are disclosed in U.S. Pat. No.
5,510,306, U.S. Pat. No. 5,082,956, and U.S. Pat. No. 5,741,759.

[0040]The isomerization and selective hydrocracking catalyst may also
comprise a modifier selected from the group consisting of lanthanum,
cerium, praseodymium, neodymium, phosphorus, samarium, gadolinium,
terbium, and mixtures thereof, as described in U.S. Pat. No. 5,716,897
and U.S. Pat. No. 5,851,949. Other suitable support materials include
ZSM-22, ZSM-23, and ZSM-35, which are described for use in dewaxing in
U.S. Pat. No. 5,246,566 and in the article entitled "New molecular sieve
process for lube dewaxing by wax isomerization," written by S. J. Miller,
in Microporous Materials 2 (1994) 439-449. The teachings of U.S. Pat. No.
4,310,440; U.S. Pat. N 4,440,871; U. 4,793,984; U.S. Pat. No. 4,758,419;
U.S. Pat. No. 4,943,424; U.S. 5,087,347; U. 5,158,665; U. 5,208,005; U.
5,246,566; U.S. Pat. No. 5,716,897; and U.S. Pat. No. 5,851,949 are
hereby incorporated by reference.

[0041]U.S. Pat. No. 5,444,032 and U.S. Pat. No. 5,608,968 teach a suitable
bifunctional catalyst which is constituted by an amorphous silica-alumina
gel and one or more metals belonging to Group VIIIA, and is effective in
the hydroisomerization of long-chain normal paraffins containing more
than 15 carbon atoms. An activated carbon catalyst support may also be
used. U.S. Pat. No. 5,981,419 and U.S. Pat. No. 5,908,134 teach a
suitable bifunctional catalyst which comprises: (a) a porous crystalline
material isostructural with beta-zeolite selected from boro-silicate
(BOR-B) and boro-alumino-silicate (Al-BOR-B) in which the molar
SiO2:Al203 ratio is higher than 300: 1; (b) one or more metal(s)
belonging to Group VIIIA, selected from platinum and palladium, in an
amount comprised within the range of from 0.05 to 5% by weight. Article
V. Calemma et al., App. Catal. A: Gen., 190 (2000), 207 teaches yet
another suitable catalyst. [0042] The isomerization and selective
hydrocracking catalyst may be any of those well known in the art such as
those described and cited above. Isomerization and selective cracking
conditions include a temperature of about 150° C. to about
360° C. and a pressure of about 1724 kPa absolute (250 psia) to
about 4726 kPa absolute (700 psia). In another embodiment the
isomerization conditions include a temperature of about 300° C. to
about 360° C. and a pressure of about 3102 kPa absolute (450 psia)
to about 3792 kPa absolute (550 psia). Other operating conditions for the
isomerization and selective hydrocracking zone are well known in the art.
Some known isomerization catalysts, when operated under more severe
conditions, also provide the selective hydrocracking catalytic function.

[0042]The isomerization and selective cracking zone effluent is processed
through one or more separation steps to obtain two purified hydrocarbon
streams, one useful as a diesel fuel or a diesel fuel blending component
and the second useful as aviation fuel or an aviation fuel blending
component. Depending upon the application, various additives may be
combined with the diesel or aviation fuel composition generated in order
to meet required specifications for different specific fuels. In
particular, the aviation fuel composition generated herein complies with,
is a blending component for, or may be combined with one or more
additives to meet at least one of: ASTM D 1655 Specification for Aviation
Turbine Fuels Defense Stan 91-91 Turbine Fuel, Aviation Kerosene Type,
Jet A-1 NATO code F-35, F-34, F-37 Aviation Fuel Quality Requirements for
Jointly Operated Systems (Joint Checklist) A combination of ASTM and Def
Stan requirements GOST 10227 Jet Fuel Specifications (Russia) Canadian
CAN/CGSB-3.22 Aviation Turbine Fuel, Wide Cut Type Canadian CAN/CGSB-3.23
Aviation Turbine Fuel, Kerosene Type MIL-DTL-83133, JP-8, MIL-DTL-5624,
JP-4, JP-5 QAV-1 (Brazil) Especifcacao de Querosene de Aviacao No. 3 Jet
Fuel (Chinese) according to GB6537 DCSEA 134A (France) Carbureacteur Pour
Turbomachines D'Aviation, Type Kerosene Aviation Turbine Fuels of other
countries, meeting the general grade requirements for Jet A, Jet A-1, Jet
B, and TS-1 fuels as described in the IATA Guidance Material for Aviation
Turbine Fuel Specifications. The aviation fuel is generally termed "jet
fuel" herein and the term "jet fuel" is meant to encompass aviation fuel
meeting the specifications above as well as to encompass aviation fuel
used as a blending component of an aviation fuel meeting the
specifications above. Additives may be added to the jet fuel in order to
meet particular specifications. One particular type of jet fuel is JP-8,
defined by Military Specification MIL-DTL-83133, which is a military
grade type of highly refined kerosene based jet propellant specified by
the United States Government. The fuel produced from glycerides or FAAs
is very similar to isoparaffinic kerosene or iPK, also known as synthetic
paraffinic kerosene (sPK) and as synthetic jet fuel.

[0043]The specifications for different types of fuels are often expressed
through acceptable ranges of chemical and physical requirements of the
fuel. As stated above, aviation turbine fuels, a kerosene type fuel
including JP-8, are specified by MIL-DTL-83133, JP-4, a blend of
gasoline, kerosene and light distillates, is specified by MIL-DTL-5624
and JP-5 a kerosene type fuel with low volatility and high flash point is
also specified by MIL-DTL-5624, with the written specification of each
being periodically revised. Often a distillation range from 10 percent
recovered to a final boiling point is used as a key parameter defining
different types of fuels. The distillations ranges are typically measured
by ASTM Test Method D 86 or D2887. Therefore, blending of different
components in order to meet a particular specification is quite common.
While the product of the present invention may have desired
characteristics and properties, it is expected that some blending of the
product with other blending components may be required to meet the
desired set of fuel specifications or future specific specifications
required for such fuels. In other words, the aviation product of this
invention is a composition which may be used with other components to
form a fuel meeting at least one of the specifications for aviation fuel
such as JP-8. The desired products are highly paraffinic distillate fuel
components having a paraffin content of at least 75% by volume.

[0044]With the effluent stream of the isomerization and selective
hydrocracking zone comprising both a liquid component and a gaseous
component, various portions of which may be recycled, multiple separation
steps may be employed. For example, hydrogen may be first separated in a
isomerization effluent separator with the separated hydrogen being
removed in an overhead stream. Suitable operating conditions of the
isomerization effluent separator include, for example, a temperature of
230° C. and a pressure of 4100 kPa absolute (600 psia). If there
is a low concentration of carbon oxides, or the carbon oxides are
removed, the hydrogen may be recycled back to the hot high pressure
hydrogen stripper for use both as a rectification gas and to combine with
the remainder as a bottoms stream. The remainder is passed to the
isomerization reaction zone and thus the hydrogen becomes a component of
the isomerization reaction zone feed streams in order to provide the
necessary hydrogen partial pressures for the reactor. The hydrogen is
also a reactant in the deoxygenation reactors, and different feedstocks
will consume different amounts of hydrogen. The isomerization effluent
separator allows flexibility for the process to operate even when larger
amounts of hydrogen are consumed in the first reaction zone. Furthermore,
at least a portion of the remainder or bottoms stream of the
isomerization effluent separator may be recycled to the isomerization
reaction zone to increase the degree of isomerization.

[0045]The remainder of the isomerization effluent after the removal of
hydrogen still has liquid and gaseous components and is cooled, by
techniques such as air cooling or water cooling and passed to a cold
separator where the liquid component is separated from the gaseous
component. Suitable operating conditions of the cold separator include,
for example, a temperature of about 20 to 60° C. and a pressure of
3850 kPa absolute (560 psia). A water byproduct stream is also separated.
At least a portion of the liquid component, after cooling and separating
from the gaseous component, may be recycled back to the isomerization
zone to increase the degree of isomerization. Prior to entering the cold
separator, the remainder of the isomerization and selective hydrocracking
zone effluent may be combined with the hot high pressure hydrogen
stripper overhead stream, and the resulting combined stream may be
introduced into the cold separator.

[0046]The liquid component contains the hydrocarbons useful as diesel fuel
or diesel fuel blending components and aviation fuel or aviation fuel
blending components, termed diesel boiling point range product and
aviation boiling point range product, respectively, as well as smaller
amounts of naphtha/gasoline and LPG. The separated liquid component is
further purified in a product distillation zone which separates lower
boiling components and dissolved gases into an LPG and naphtha/gasoline
stream; an aviation range product; and a diesel range product. Suitable
operating conditions of the product distillation zone include a
temperature of from about 20 to about 200° C. at the overhead and
a pressure from about 0 to about 1379 kPa absolute (0 to 200 psia). The
conditions of the distillation zone may be adjusted to control the
relative amounts of hydrocarbon contained in the aviation range product
stream and the diesel range product stream.

[0047]The LPG and naphtha/gasoline stream may be further separated in a
debutanizer or depropanizer in order to separate the LPG into an overhead
stream, leaving the naphtha/gasoline in a bottoms stream. Suitable
operating conditions of this unit include a temperature of from about 20
to about 200° C. at the overhead and a pressure from about 0 to
about 2758 kPa absolute (0 to 400 psia). The LPG may be sold as valuable
product or may be used in other processes such as a feed to a hydrogen
production facility. Similarly, the naphtha/gasoline may be used in other
processes, such as the feed to a hydrogen production facility.

[0048]The gaseous component separated in the product separator comprises
mostly hydrogen and the carbon dioxide from the decarboxylation reaction.
Other components such as carbon monoxide, propane, and hydrogen sulfide
or other sulfur containing component may be present as well. It is
desirable to recycle the hydrogen to the isomerization zone, but if the
carbon dioxide was not removed, its concentration would quickly build up
and effect the operation of the isomerization zone. The carbon dioxide
can be removed from the hydrogen by means well known in the art such as
reaction with a hot carbonate solution, pressure swing absorption, etc.
Amine absorbers may be employed as taught in copending U.S. Pat. No.
applications U.S. application Ser. No. 12/193,176 and U.S. application
Ser. No. 12/193,196, hereby incorporated by reference. If desired,
essentially pure carbon dioxide can be recovered by regenerating the
spent absorption media.

[0049]Similarly, a sulfur containing component such as hydrogen sulfide
may be present to maintain the sulfided state of the deoxygenation
catalyst or to control the relative amounts of the decarboxylation
reaction and the hydrogenation reaction that are both occurring in the
deoxygenation zone. The amount of sulfur is generally controlled and so
must be removed before the hydrogen is recycled. The sulfur components
may be removed using techniques such as absorption with an amine or by
caustic wash. Of course, depending upon the technique used, the carbon
dioxide and sulfur containing components, and other components, may be
removed in a single separation step such as a hydrogen selective
membrane.

[0050]The hydrogen remaining after the removal of at least carbon dioxide
may be recycled to the reaction zone where hydrogenation primarily occurs
and/or to any subsequent beds or reactors. The recycle stream may be
introduced to the inlet of the reaction zone and/or to any subsequent
beds or reactors. One benefit of the hydrocarbon recycle is to control
the temperature rise across the individual beds. However, as discussed
above, the amount of hydrocarbon recycle may be determined based upon the
desired hydrogen solubility in the reaction zone which is in excess of
that used for temperature control. Increasing the hydrogen solubility in
the reaction mixture allows for successful operation at lower pressures,
and thus reduced cost.

[0051]As discussed above, at least a portion of the diesel boiling point
range product; at least a portion of the aviation boiling point range
product, at least a portion of the LPG and naphtha/gasoline stream; at
least a portion of a naphtha/gasoline stream or an LPG stream generated
by separating the LPG and naphtha/gasoline stream into an LPG stream and
the naphtha/gasoline stream; or any combination thereof may be recycled
to the optional rectification zone of the hot high pressure hydrogen
stripper.

[0052]The following embodiment is presented in illustration of this
portion of the process to generate the paraffin rich component and is not
intended as an undue limitation on the generally broad scope of the
invention as set forth in the claims.

[0053]Turning to FIG. 1, the process for generating the paraffin rich
component begins with a renewable feedstock stream 2 which may pass
through an optional feed surge drum. The feedstock stream is combined
with recycle gas stream 68 and recycle stream 16 to form combined feed
stream 20, which is heat exchanged with reactor effluent and then
introduced into deoxygenation reactor 4. The heat exchange may occur
before or after the recycle is combined with the feed. Deoxygenation
reactor 4 may contain multiple beds shown in FIG. 2 as 4a, 4b and 4c.
Deoxygenation reactor 4 contains at least one catalyst capable of
catalyzing decarboxylation and/or hydrodeoxygenation of the feedstock to
remove oxygen. Deoxygenation reactor effluent stream 6 containing the
products of the decarboxylation and/or hydrodeoxygenation reactions is
removed from deoxygenation reactor 4 and heat exchanged with stream 20
containing feed to the deoxygenation reactor. Stream 6 comprises a liquid
component containing largely normal paraffin hydrocarbons in the diesel
boiling point range and a gaseous component containing largely hydrogen,
vaporous water, carbon monoxide, carbon dioxide and propane.

[0054]Deoxygenation reactor effluent stream 6 is then directed to hot high
pressure hydrogen stripper 8. Make up hydrogen in line 10 is divided into
two portions, stream 10a and 10b. Make up hydrogen in stream 10a is also
introduced to hot high pressure hydrogen stripper 8. In hot high pressure
hydrogen stripper 8, the gaseous component of deoxygenation reactor
effluent 6 is selectively stripped from the liquid component of
deoxygenation reactor effluent 6 using make-up hydrogen 10a and recycle
hydrogen 28. The dissolved gaseous component comprising hydrogen,
vaporous water, carbon monoxide, carbon dioxide and at least a portion of
the propane, is selectively separated into hot high pressure hydrogen
stripper overhead stream 14. The remaining liquid component of
deoxygenation reactor effluent 6 comprising primarily normal paraffins
having a carbon number from about 8 to about 24 with a cetane number of
about 60 to about 100 is removed as hot high pressure hydrogen stripper
bottom 12.

[0055]A portion of hot high pressure hydrogen stripper bottoms forms
recycle stream 16 and is combined with renewable feedstock stream 2 to
create combined feed 20. Another portion of recycle stream 16, optional
stream 16a, may be routed directly to deoxygenation reactor 4 and
introduced at interstage locations such as between beds 4a and 4b and or
between beds 4b and 4c in order, or example, to aid in temperature
control. The remainder of hot high pressure hydrogen stripper bottoms in
stream 12 is combined with hydrogen stream 10b to form combined stream 18
which is routed to isomerization and selective hydrocracking reactor 22.
Stream 18 may be heat exchanged with isomerization reactor effluent 24.

[0056]The product of the isomerization and selective hydrocracker reactor
containing a gaseous portion of hydrogen and propane and a
branched-paraffin-enriched liquid portion is removed in line 24, and
after optional heat exchange with stream 18, is introduced into hydrogen
separator 26. The overhead stream 28 from hydrogen separator 26 contains
primarily hydrogen which may be recycled back to hot high pressure
hydrogen stripper 8. Bottom stream 30 from hydrogen separator 26 is air
cooled using air cooler 32 and introduced into product separator 34. In
product separator 34 the gaseous portion of the stream comprising
hydrogen, carbon monoxide, hydrogen sulfide, carbon dioxide and propane
are removed in stream 36 while the liquid hydrocarbon portion of the
stream is removed in stream 38. A water byproduct stream 40 may also be
removed from product separator 34. Stream 38 is introduced to product
stripper 42 where components having higher relative volatilities are
separated into stream 44, components within the boiling range of aviation
fuel is removed in stream 45, with the remainder, the diesel range
components, being withdrawn from product stripper 42 in line 46.
Optionally, a portion of the diesel range components in line 46 are
recycled in line 46a to hot high pressure hydrogen stripper 8 optional
rectification zone 23 and used as an additional rectification agent.
Stream 44 is introduced into fractionator 48 which operates to separate
LPG into overhead 50 leaving a naphtha/gasoline bottoms 52. Any of
optional lines 72, 74, or 76 may be used to recycle at least a portion of
the isomerization zone effluent back to the isomerization zone to
increase the amount of n-paraffins that are isomerized to branched
paraffins.

[0057]The vapor stream 36 from product separator 34 contains the gaseous
portion of the isomerization effluent which comprises at least hydrogen,
carbon monoxide, hydrogen sulfide, carbon dioxide and propane and is
directed to a system of amine absorbers to separate carbon dioxide and
hydrogen sulfide from the vapor stream. Because of the cost of hydrogen,
it is desirable to recycle the hydrogen to deoxygenation reactor 4, but
it is not desirable to circulate the carbon dioxide or an excess of
sulfur containing components. In order to separate sulfur containing
components and carbon dioxide from the hydrogen, vapor stream 36 is
passed through a system of at least two amine absorbers, also called
scrubbers, starting with the first amine absorber zone 56. The amine
chosen to be employed in first amine scrubber 56 is capable of
selectively removing at least both the components of interest, carbon
dioxide and the sulfur components such as hydrogen sulfide. Suitable
amines are available from DOW and from BASF, and in one embodiment the
amines are a promoted or activated methyldiethanolamine (MDEA). See U.S.
Pat. No. 6,337,059, hereby incorporated by reference in its entirety.
Suitable amines for the first amine absorber zone from DOW include the
UCARSOL® AP series solvents such as AP802, AP804, AP806, AP810 and
AP814. The carbon dioxide and hydrogen sulfide are absorbed by the amine
while the hydrogen passes through first amine scrubber zone and into line
68 to be recycled to the first reaction zone. The amine is regenerated
and the carbon dioxide and hydrogen sulfide are released and removed in
line 62. Within the first amine absorber zone, regenerated amine may be
recycled for use again. The released carbon dioxide and hydrogen sulfide
in line 62 are passed through second amine scrubber zone 58 which
contains an amine selective to hydrogen sulfide, but not selective to
carbon dioxide. Again, suitable amines are available from DOW and from
BASF, and in one embodiment the amines are a promoted or activated MDEA.
Suitable amines for the second amine absorber zone from DOW include the
UCARSOL® HS series solvents such as HS101, HS 102, HS103, HS104,
HS115. Therefore the carbon dioxide passes through second amine scrubber
zone 58 and into line 66. The amine may be regenerated which releases the
hydrogen sulfide into line 60. Regenerated amine is then reused, and the
hydrogen sulfide may be recycled to the deoxygenation reaction zone.
Conditions for the first scrubber zone includes a temperature in the
range of 30 to 60° C. The first absorber is operated at
essentially the same pressure as the reaction zone. By "essentially" it
is meant that the operating pressure of the first absorber is within
about 1034 kPa absolute (150 psia) of the operating pressure of the
reaction zone. For example, the pressure of the first absorber is no more
than 1034 kPa absolute (150 psia) less than that of the reaction zone.
The second amine absorber zone is operated in a pressure range of from
138 kPa absolute (20 psia) to 241 kPa absolute (35 psia). Also, at least
the first the absorber is operated at a temperature that is at least
1° C. higher than that of the separator. Keeping the absorbers
warmer than the separator operates to maintain any light hydrocarbons in
the vapor phase and prevents the light hydrocarbons from condensing into
the absorber solvent.

[0058]It is readily understood that instead of a portion of the diesel
range components in line 46 being optionally recycled in line 46a to hot
high pressure hydrogen stripper 8 optional rectification zone 23 and used
as a rectification agent, a portion of naphtha/gasoline bottoms 52 is
optionally recycled to hot high pressure hydrogen stripper 8 optional
rectification zone 23 and used as a rectification agent. Similarly,
instead of a portion of the diesel range components in line 46 being
optionally recycled in line 46a to hot high pressure hydrogen stripper 8
optional rectification zone 23 and used as a rectification agent, the
diesel range components in line 46a and portion of naphtha/gasoline
bottoms 52 combined to form a rectification agent stream which is
optionally recycled to hot high pressure hydrogen stripper 8 optional
rectification zone 23 and used as a rectification agent.

[0059]Minimizing the amount of normal paraffins that bypass the
isomerization and selective hydrocracking zone helps to meet freeze point
specifications for many aviation fuels without having to significantly
lower the quantity of aviation fuel produced. Normal paraffins that
bypass the isomerization and selective hydrocracking zone are not
isomerized and the normal paraffins generally have higher freeze points
than the corresponding isomerized paraffins. To demonstrate the success
of the optional rectification zone, the invention both including and not
including the rectification zone in the hot high pressure hydrogen
stripper was simulated in a model simulation. In the simulations, a
maximum distillate production was set and a -10° C. cloud point
target for the diesel range product was set. In the simulation where the
optional rectification zone was not employed, the overall percentage of
hydrocarbons in the aviation range plus the diesel range that bypassed
the isomerization and selective cracking zone via the hot high pressure
hydrogen stripper overhead stream was determined to be 4.95 mass-% and
the percentage of hydrocarbons in the aviation range that bypassed the
isomerization and selective cracking zone via the hot high pressure
hydrogen stripper overhead stream was determined to be 5.45 mass-%. The
simulation was repeated, this time using the optional rectification zone
in the hot high pressure hydrogen stripper as shown in FIG. 1. In this
simulation, the overall percentage of hydrocarbons in the aviation range
plus the diesel range that bypassed the isomerization and selective
cracking zone via the hot high pressure hydrogen stripper overhead stream
was determined to be 1.12 mass-% and the percentage of hydrocarbons in
the aviation range that bypassed the isomerization and selective cracking
zone via the hot high pressure hydrogen stripper overhead stream was
determined to be 4.07 mass-%. The result of this change corresponds to
either a reduction of aviation fuel product freeze point of 7° C.
at a constant aviation fuel product yield of 10.4 mass-%, or an increase
in aviation fuel production of 9 mass-% at a constant -40° C.
freeze point.

Example of Paraffin Rich Component

[0060]Deoxygenation of refined canola oil over the deoxygenation catalyst
CAT-DO was accomplished by mixing the canola oil with a 2500 ppm S
co-feed and flowing the mixture down over the catalyst in a tubular
furnace at conditions of about 330° C., 3447 kPa gauge (500 psig),
LHSV of 1 h-1 and an H2/feed ratio of about 4000 scf/bbl. The
soybean oil was completely deoxygenated and the double bonds hydrogenated
to produce an n-paraffin mixture having predominantly from about 15 to
about 18 carbon atoms; deoxygenation products CO, CO2, H2O, and
propane; with removal of the sulfur as H2S.

[0061]The n-paraffin product from the deoxygenation stage was fed over a
selective cracking/isomerization catalyst in a second process step. The
n-paraffin mixture was delivered down flow over the selective
cracking/isomerization catalyst in a tubular furnace at conditions of
about 355° C., 4140 kPa gauge (600 psig), 1.0 LHSV and an
H2/feed ratio of about 2100 scf/bbl. The product from this selective
cracking and isomerization step was fractionated and the jet fuel range
material (as defined in the specification for JP-8, MIL-DTL-83133) was
collected. After fractionation, the two stage process produced 18 wt.-%
jet fuel-range paraffms with a high iso/normal ratio. The properties of
final jet fuel produced are shown in Table 1.

[0062]The cyclic rich component may be one or more hydrocarbon streams, a
diesel boiling point range product, an aviation boiling point range
product, and a naphtha/gasoline boiling point range product from
renewable feedstocks such as feedstocks originating from plants or
animals. The term "rich" is meant to indicate at least 40 mass-%. The
term renewable feedstock is meant to include feedstocks other than those
obtained from petroleum crude oil. Suitable feedstocks include any of
glycerides, free fatty acids, free fatty alkyl esters, biomass,
lignocellulose (including lignin, cellulose, and hemicellulose), free
sugars, and combinations thereof.

[0063]Multiple routes for generating the paraffin rich component above.
Each of those route may also be used to generate the cyclic component by
further treating the paraffin with a cyclization or aromatization
catalyst to produce aromatics and naphthenes. The UOP Platforming process
converts naphtha to aromatics and naphthenes suitable for blending into
gasoline and aviation fuel, see Dachos, N.; Kelley A.; Felch, D.; Reis,
E. UOP Platforming Process pp. 4.3-4.26 in Handbook of Petroleum
processes, ed. Robert A. Meyers, McGraw-Hill. Therefore, some routes for
the generation of the cyclic component include: deoxygenation,
isomerization, and cyclization; gasification followed by oligomerization
and cyclization; deoxygenation, isomerization, hydrocracking and
cyclization; oligomerization, deoxygenation and cyclization;
deoxygenation, cyclization, and aromatization; gasification followed by
oligomerization, cyclization, and aromatization; deoxygenation,
hydrocracking, cyclization, and aromatization; deoxygenation,
isomerization, and hydrocracking, cyclization, and aromatization.

[0065]Further routes involves the generation of synthesis gas from the
gasification of biomass, conversion of the synthesis gas to light
oxygenates such as alcohols, and conversion of the light oxygenates to
paraffins, dehydration of the paraffins to olefins and then olefin
cyclooligomerization. Another route involves the generation of synthesis
gas from the gasification of biomass, conversion of the synthesis gas to
light oxygenates such as alcohols, and conversion of the light oxygenates
to a mixed hydrocarbon stream comprising cycloparaffins and aromatics.
The methanol to gasoline route may be employed.

[0066]The biomass undergoes fermentation to generate light oxygenates
which are then dehydrogenated to olefins which undergo olefin
cyclooligomerization to form the cyclics. Another route involves
fermentation of biomass to generate light oxygenates with the light
oxygenates being converted to a mixed hydrocarbon stream comprising
cycloparaffins and aromatics. The methanol to gasoline route may be
employed.

[0067]The following discussion is a detailed description of one embodiment
of the generation of a cyclic rich component. The cyclic rich component
may be one or more hydrocarbon streams, a diesel boiling point range
product, an aviation boiling point range product, and a gasoline and
naphtha/gasoline boiling point range product from renewable feedstocks
such as feedstocks originating from lignocellulose. The term "rich" is
meant to indicate at least 40 mass-%. In the U.S. and worldwide, there
are huge amounts of lignocellulosic material, or biomass, which is not
utilized, but is left to decay, often in a landfill, or just in an open
field or forest. The material includes large amounts of wood waste
products, and leaves and stalks of crops or other plant material that is
regularly discarded and left to decay in fields. The emergence of
inedible lipid-bearing crops for the production of renewable diesel will
also produce increased amounts of biomass post extraction, often known as
meal. Growth of cellulosic ethanol will also produce large amounts of a
lignin side product. Biomass includes, but is not limited to, lignin,
plant parts, fruits, vegetables, plant processing waste, wood chips,
chaff, grain, grasses, corn, corn husks, weeds, aquatic plants, hay,
meal, paper, paper products, recycled paper and paper products, and any
cellulose containing biological material or material of biological
origin. This biomass material can be pyrolyzed to make a pyrolysis oil,
but due to poor thermal stability, the high water content of the
pyrolysis oil, often greater than 25%, high total acid number often
greater than 100, low heating value, and phase incompatibility with
petroleum based materials, pyrolysis oil has found little use as a fuel.

[0068]This portion of the process substantially converts the pyrolysis oil
from biomass into the cyclic rich component which may be
naphtha/gasoline, aviation, and diesel boiling range components, having
low acidity, low water, low oxygen, and low sulfur content. The pyrolysis
of the biomass to form the pyrolysis oil is achieved by any technique
known in the art, see for example, Mohan, D.; Pittman, C. U.; Steele, P.
H. Energy and Fuels, 2006, 20, 848-889. Once the pyrolysis oil is
generated from the biomass, although optional, it is not necessary to
separate the pyrolytic lignin from the pyrolysis oil before further
processing, thereby eliminating a step previously employed in industry.
The whole pyrolysis oil may be processed, without a portion of the
aqueous phase being removed to enrich the pyrolysis oil in the pyrolytic
lignin. The pyrolytic lignin contains potentially high value products in
the form of aromatic and naphthenic compounds having complex structures
that comprises aromatic rings that are linked by oxygen atoms or carbon
atoms. These structures can be broken into smaller segments when
decarboxylated, decarbonylated, or hydrodeoxygenated, while maintaining
the aromatic ring structures. One desired product is at least one cyclic
hydrocarbon-rich stream. However, this processing of the pyrolytic lignin
may be accomplished in the presence of the rest of the pyrolysis oil and
no separation of the pyrolytic lignin before processing is required.
Pyrolytic lignin is a pyrolysis product of the lignin portion of biomass.
It can be separated from the rest of the whole pyrolysis oil during the
pyrolysis process or through post-processing to produce an additional
aqueous phase, which includes pyrolysis products primarily from the
cellulose and hemicellulose portion of the biomass. The pyrolysis process
can convert all components in the biomass feedstock into products useful
as fuels or fuel components after full deoxygenation of the pyrolysis oil
product. The water soluble components can also be transformed to
naphthenes and aromatics under pyrolysis conditions. The production of
heavier molecular weight products is known from steam cracking technology
to produce light olefins, also run under pyrolysis conditions. Even feeds
such as ethane, propane, and light naphtha/gasoline produce heavier side
products in these thermal cracking processes. The amount of these heavier
products depends on the conditions of the thermal cracking reactor.
Optionally, the pyrolysis oil may be separated and only a portion of the
pyrolysis oil be introduced to the partial deoxygenation zone.

[0069]The pyrolysis oil is fully deoxygenated in two separate zones, a
partial deoxygenation zone and a full deoxygenation zone. The partial
deoxygenation zone may also be considered to be a hydrotreating zone and
the full deoxygenation zone may be considered to be a hydrocracking zone.
"Full" deoxygenation is meant to include deoxygenating at least 99% of
available oxygenated hydrocarbons. The zones will primarily be referred
to herein as a partial deoxygenation zone and a full deoxygenation zone.
In the partial deoxygenation zone, partial deoxygenation occurs at milder
conditions than the full deoxygenation zone and uses a catalyst such as a
hydrotreating catalyst. In general, the partial oxidation zone removes
the most reactive and thermally instable oxygenates. The oxygen level of
the pyrolysis oil feedstock, which typically ranges from about 35 wt. %
to about 60 wt %, is reduced to a significantly lower level, from about 5
wt. % to about 20 wt. % in the partial deoxygenation zone. Water is
reduced from pyrolysis oil feedstock levels from about 10 wt. % to about
40 wt. % to levels from about 2 wt. % to about 11 wt. %. The acidity is
greatly reduced as well in the partial deoxygenation zone, from a TAN
level of about 125 to about 200 in the pyrolysis oil feedstock to a
reduced level from about 40 to about 100 in the partial deoxygenation
zone effluent.

[0070]The more thermally stable effluent from the partial deoxygenation
zone can then be fully deoxygenated in the full deoxygenation zone. In
the full deoxygenation zone, a hydrocracking catalyst, which has higher
activity as compared to the hydrotreating catalyst, is employed with the
option of more severe process conditions in order to catalyze the
deoxygenation of less reactive oxygenates. Some hydrocracking of
feedstock molecules will also occur to a higher extent than in the
partial deoxygenation zone. In the full deoxygenation zone, oxygen
content is reduced from about 5 wt. % to about 20 wt. % to much lower
levels, from ppm concentrations to about 0.5 wt. %. Water is also greatly
reduced in the full deoxygenation zone, from about 2 wt. % to about 11
wt. % down to levels from about 100 ppm to about 1000 ppm. The acidity is
greatly reduced from initial TAN levels of about 40 to about 100 mg KOH/g
oil to lower levels from about 0.5 to about 4 mg KOH/g oil. The effluent
of the full deoxygenation zone is a hydrocarbon mixture rich in
naphthenes and aromatics.

[0071]In one embodiment, as shown in FIG. 2, pyrolysis oil 110 is not
separated and enters partial deoxygenation zone 112 along with recycle
hydrogen stream 154 and optional hydrocarbon recycle 156 where contact
with a deoxygenation and hydrogenation catalyst at deoxygenation
conditions generates partially deoxygenated pyrolysis oil stream 114. The
deoxygenation zone 112 performs catalytic decarboxylation,
decarbonylation, and hydrodeoxygenation of oxygen polymers and single
oxygenated molecules in the pyrolysis oil by breaking the oxygen
linkages, and forming water and CO2 from the oxygen and leaving
smaller molecules. For example, the phenylpropyl ether linkages in the
pyrolytic lignin will be partially deoxygenated producing some aromatic
rings, such as alkylbenzenes and polyalkylbenzenes. Very reactive
oxygenates will be deoxygenated as well, including small molecular weight
carboxylic acids therefore greatly increasing the thermal stability of
the product. Pyrolysis oil components not derived from lignin, including
cellulose, hemicellulose, free sugars, may yield products such as acetic
acid, furfural, furan, levoglucosan, 5-hydroxymethylfurfural,
hydroxyacetaldhyde, formaldehyde, and others such as those described in
Mohan, D.; Pittman, C. U.; Steele, P. H. Energy and Fuels, 2006, 20,
848-889. Therefore, pyrolysis oil components not derived from lignin will
also be partially or fully deoxygenated with the carbohydrates giving
primarily light hydrocarbon fractions and water. The light hydrocarbon
fractions may contain hydrocarbons with six or fewer carbon atoms. The
reactions of decarbonylation, decarboxylation and hydrodeoxygenation are
collectively referred to as deoxygenation reactions. Hydrogenation of
olefins also occur in this zone. The catalysts and conditions of partial
deoxygenation zone 112 are selected so that the more reactive compounds
are deoxygenated. The effluent of partial deoxygenation zone is a
partially deoxygenated pyrolysis oil stream 114 that has increased
thermal stability as compared to the feed pyrolysis oil.

[0072]Partially deoxygenated pyrolysis oil stream 114 is passed to a
separation zone 116. Carbon oxides, possibly hydrogen sulfide, and C3 and
lighter components are separated and removed in overhead line 120 and a
partially deoxygenated product stream 118 is removed from separation zone
116. Separation zone 116 may comprise a separator. Depending upon whether
the separator is operated in a hot or cold mode, the water may be removed
as a vapor in line 120 (hot separator mode) or as a liquid in line 122
(cold separator mode). Overhead line 120 comprises a large quantity of
hydrogen and at least the carbon dioxide from the decarboxylation
reaction. The carbon dioxide can be removed from the hydrogen by means
well known in the art such as reaction with a hot carbonate solution,
pressure swing absorption, etc. Also, absorption with an amine in
processes such as described in co-pending applications U.S. application
Ser. No. 12/193,176 and U.S. application Ser. No. 12/193,196, hereby
incorporated by reference, may be employed. If desired, essentially pure
carbon dioxide can be recovered by regenerating the spent absorption
media. Therefore overhead line 120 is passed through one or more
scrubbers 144 such as amine scrubbers to remove carbon dioxide in line 46
and hydrogen sulfide in line 148. Depending upon the scrubber technology
selected some portion of water may also be retained by the scrubber. The
lighter hydrocarbons and gasses, possibly including a portion of water,
are conducted via line 150 to steam reforming zone 152. In one embodiment
the light hydrocarbon fractions may contain hydrocarbons with six or
fewer carbon atoms. After purification, hydrogen generated in steam
reforming zone 152 is conducted via line 154 to combine with feedstock
110 and partially deoxygenated product stream 118. The hydrogen may be
recycled to combine with the feedstock as shown or may be introduced
directly to the reaction zone where hydrogenation primarily occurs and/or
to any subsequent reactor beds.

[0073]The partially deoxygenated product stream 118 along with recycle
hydrogen stream 154 and optional hydrocarbon recycle 156, is passed to a
second hydrodeoxygenation zone 124, where the remaining oxygen is
removed. Full deoxygenation zone 124 performs catalytic decarboxylation,
decarbonylation, and hydrodeoxygenation of the remaining oxygen compounds
that are more stable than those reacted in the first stage. Therefore, a
more active catalyst and more severe process conditions are employed in
full deoxygenation zone 124 as compared to partial deoxygenation zone 112
in order to catalyze full deoxygenation.

[0074]Full deoxygenation zone effluent 126 is introduced to phase
separator 128. Carbon oxides, possibly hydrogen sulfide and C3 and
lighter components are separated and removed in line 30 and liquid
hydrocarbons are removed in line 132. Depending upon whether the
separator is operated in a hot or cold mode, the water may be removed as
a vapor in line 130 (hot separator mode) or as a liquid in line 158 (cold
separator mode). The overhead in line 130 comprises a large quantity of
hydrogen and the carbon dioxide from the decarboxylation reaction. The
carbon dioxide can be removed from the hydrogen by means well known in
the art, reaction with a hot carbonate solution, pressure swing
absorption, etc. Also, absorption with an amine in processes such as
described in co-pending applications U.S. application Ser. No. 12/193,196
and U.S. application Ser. No. 12/193,176, hereby incorporated by
reference, may be employed. If desired, essentially pure carbon dioxide
can be recovered by regenerating the spent absorption media. Therefore
line 130 is passed through one or more scrubbers 144 such as amine
scrubbers to remove carbon dioxide in line 146 and hydrogen sulfide in
line 148. Depending upon the scrubber technology selected some portion of
water may also be retained by the scrubber. The lighter hydrocarbons and
gasses, possibly including a portion of water, are conducted via line 150
to steam reforming zone 152. A liquid stream containing hydrocarbons is
removed from separator 128 in line 132 and conducted to product
fractionation zone 134. Product fractionation zone 134 is operated so
that product cut 136 contains the hydrocarbons in a boiling range most
beneficial to meeting the gasoline specifications. Product cut 138 is
collected for use as aviation fuel or as a blending component of aviation
fuel. The lighter materials such as naphtha/gasoline and LPG are removed
in fractionation zone overhead stream 160. A portion of stream 160 may be
optionally conducted in line 162 to the steam reforming zone 152. If
desired, the naphtha/gasoline and LPG may be further separated into an
LPG stream and a naphtha/gasoline stream (not shown).

[0075]Hydrocarbons that have a boiling point higher than acceptable for
the specification of the aviation fuel are removed in bottoms stream 140.
A portion of bottoms stream 140 may be recovered and used as fuel such
as, for example, low sulfur heating oil fuel. It is likely that bottoms
stream 140 may be acceptable for use as diesel or a diesel blending
component. Alternatively, bottoms stream 140 could be upgraded to diesel
in a separate process. A portion of bottoms stream 140 is optionally
recycled to partial deoxygenation zone 112 and/or full deoxygenation
reaction zone 124.

[0076]The cyclic rich component may be any of streams 132, 136, 138, 160,
or any mixture thereof.

[0077]A portion of a hydrocarbon stream may also be cooled down if
necessary and used as cool quench liquid between beds of one of the
deoxygenation zones, or between the first and the full deoxygenation zone
to further control the heat of reaction and provide quench liquid for
emergencies. The recycle stream may be introduced to the inlet of one or
both of the reaction zones and/or to any subsequent beds or reactors. One
benefit of the hydrocarbon recycle is to control the temperature rise
across the individual beds. However, as discussed within, the amount of
hydrocarbon recycle may be is determined based upon the desired hydrogen
solubility in the reaction zone. Increasing the hydrogen solubility in
the reaction mixture allows for successful operation at lower pressures,
and thus reduced cost. Operating with high recycle and maintaining high
levels of hydrogen in the liquid phase helps dissipate hot spots at the
catalyst surface and reduces the formation of undesirable heavy
components which lead to coking and catalyst deactivation. The
fractionation zone may contain more than one fractionation column and
thus the locations of the different streams separated may vary from that
shown in the figures.

[0078]In another embodiment, the pyrolysis oil feed stream is separated to
remove at least a portion of the aqueous phase thereby concentrating the
amount of pyrolytic lignin left in the pyrolysis oil and generating a
pyrolytic lignin-enriched pyrolysis oil. The separation may be
accomplished by passing the pyrolysis oil through a phase separator where
it is separated into an aqueous phase and a pyrolytic lignin phase and
removing at least a portion of the aqueous phase.

[0079]In another embodiment, both deoxygenation zones are housed in a
single reactor. The deoxygenation zones may be combined through the use
of a multifunctional catalyst capable of deoxygenation and hydrogenation
or a set of catalysts. Or a reactor housing two separate zones, such as a
stacked bed reactor, may be employed. For example, partial deoxygenation
and hydrogenation can occur over the first catalyst in a first portion of
a reactor, a first zone, while full deoxygenation occurs with a more
active catalyst in a second portion the reactor, a second zone. A stacked
bed configuration may be advantageous because a less active catalyst in
an upper zone will deoxygenate the most reactive oxygen compounds without
generating exotherms that can promote the formation of thermal coke.

[0080]Hydrogen is needed for the deoxygenation and hydrogenation reactions
above, and to be effective, a sufficient quantity of hydrogen must be in
solution in the deoxygenation zone to most effectively take part in the
catalytic reaction. If hydrogen is not available at the reaction site of
the catalyst, the coke forms on the catalyst and deactivates the
catalyst. High operating pressures may be used in order to achieve a
desired amount of hydrogen in solution and readily available for reaction
and to avoid coking reactions on the catalyst. However, higher pressure
operations are more costly to build and to operate as compared to their
lower pressure counterparts.

[0081]The desired amount of hydrogen may be kept in solution at lower
pressures by employing a large recycle of hydrocarbon. An added benefit
is the control of the temperature in the deoxygenation zone(s) since the
deoxygenation reactions are exothermic reactions. However, the range of
recycle to feedstock ratios used herein is set based on the need to
control the level of hydrogen in the liquid phase and therefore reduce
the deactivation rate of the catalyst. The amount of recycle is
determined not on temperature control requirements, but instead, based
upon hydrogen solubility requirements. Hydrogen has a greater solubility
in the hydrocarbon product than it does in the pyrolysis oil feedstock or
the portion of the pyrolysis oil feedstock after separation. By utilizing
a large hydrocarbon recycle the solubility of hydrogen in the liquid
phase in the reaction zone is greatly increased and higher pressures are
not needed to increase the amount of hydrogen in solution and avoid
catalyst deactivation at low pressures. The hydrocarbon recycle may be a
portion of the stream in any of lines 132, 140, 138, or 136, or any
combination thereof, and the hydrocarbon recycle is directed to
deoxygenation zone 112. The figure shows optional hydrocarbon recycle 156
as a portion of diesel boiling point range component 140. However it is
understood that in other embodiments portions different streams or
combinations of stream such as the product stream 132 or any of
fractionation zone streams 138, 136, 160 may be used as the hydrocarbon
recycle. Suitable volume ratios of hydrocarbon recycle to pyrolysis oil
feedstock is from about 2:1 to about 8:1. In another embodiment the ratio
is in the range of about 3:1 to about 6:1 and in yet another embodiment
the ratio is in the range of about 4:1 to about 5:1.

[0082]Furthermore, the rate of reaction in the deoxygenation zone is
increased with the hydrocarbon recycle resulting in a greater amount of
throughput of material through the reactor in a given period of time.
Lower operating pressures provide an additional advantage in increasing
the decarboxylation reaction while reducing the hydrodeoxygenation
reaction. The result is a reduction in the amount of hydrogen required to
remove oxygen from the feedstock component and produce a finished
product. Hydrogen can be a costly component of the feed and reduction of
the hydrogen requirements is beneficial from an economic standpoint.

[0083]In another embodiment, mixtures or co-feeds of the pyrolysis oil and
other renewable feedstocks or petroleum derived hydrocarbons may also be
used as the feedstock to the deoxygenation zone. The mixture of the
pyrolysis oil and another renewable feedstock or a petroleum derived
hydrocarbon is selected to result in greater hydrogen solubility. Other
feedstock components which may be used as a co-feed component in
combination with the pyrolysis oil from the above listed biomass
materials, include spent motor oil and industrial lubricants, used
paraffin waxes, liquids derived from gasification of coal, biomass, or
natural gas followed by a downstream liquefaction step such as
Fischer-Tropsch technology; liquids derived from depolymerization,
thermal or chemical, of waste plastics such as polypropylene, high
density polyethylene, and low density polyethylene; and other synthetic
oils generated as byproducts from petrochemical and chemical processes.
One advantage of using a co-feed component is the transformation of what
has been considered to be a waste product from a petroleum based or other
process into a valuable co-feed component to the current process.

[0084]The partial deoxygenation zone is operated at a pressure from about
3.4 MPa (500 psia) to about 14 MPa (3000 psia), and preferably is
operated at a pressure from about 3.4 MPa (500 psia) to about 12 MPa
(1800 psia). The partial deoxygenation zone is operated at a temperature
from about 200° C. to 400° C. with one embodiment being
from about 300° C. to about 375° C. The partial
deoxygenation zone is operated at a space velocity from about 0.1 LHSV
h-1 to 1.5 LHSV h-1 based on pyrolysis oil feedstock; this
space velocity range does not include any contribution from a recycle
stream. In one embodiment the space velocity is from about 0.25 to about
1.0 LHSV h-1. The hydrogen to liquid hydrocarbon feed ratio is at
about 889 to about 3,555 std m3/m3 (about 5000 to 20,000
scf/bbl) with one embodiment being from about 1,778 to about 2,666 std
m3/m3 (about 10,000 to 15,000 scf/bbl). The catalyst in the
partial deoxygenation zone is any hydrogenation and hydrotreating
catalysts well known in the art such as nickel or nickel/molybdenum
dispersed on a high surface area support. Other hydrogenation catalysts
include one or more noble metal catalytic elements dispersed on a high
surface area support. Non-limiting examples of noble metals include Pt
and/or Pd dispersed on gamma-alumina or activated carbon. Another example
includes the catalysts disclosed in U.S. Pat. No. 6,841,085, hereby
incorporated by reference.

[0085]In the full deoxygenation zone, the conditions are more severe and
the catalyst more active compared to that of the partial deoxygenation
zone. The catalyst is any hydrocracking catalyst, having a hydrocracking
function, that is well known in the art such as nickel or
nickel/molybdenum dispersed on a high surface area support. Another
example is a combined zeolitic and amorphous silica-aluminas catalyst
with a metal deposited on the catalyst. The catalyst includes at least
one metal selected from nickel (Ni), chromium (Cr), molybdenum (Mo),
tungsten (W), cobalt (Co), rhodium (Rh), iridium (Ir), ruthenium (Ru),
and rhenium (Re). In one embodiment, the catalyst includes a mixture of
the metals Ni and Mo on the catalyst. The catalyst is preferably a large
pore catalyst that provides sufficient pore size for allowing larger
molecules into the pores for cracking to smaller molecular constituents.
The metal content deposited on the catalysts used are deposited in
amounts ranging from 0.1 wt. % to 20 wt. %, with specific embodiments
having values for the metals including, but not limited to, nickel in a
range from 0.5 wt. % to 10 wt. %, tungsten in a range from 5 wt. % to 20
wt. %, and molybdenum in a range from 5 wt. % to 20 wt. %. The metals can
also be deposited in combinations on the catalysts with example
combinations being Ni with W, and Ni with Mo. Zeolites used for the
catalysts include, but are not limited to, beta zeolite, Y-zeolite, MFI
type zeolites, mordenite, silicalite, SM3, and faujasite. The catalysts
are capable of catalyzing decarboxylation, decarbonylation and/or
hydrodeoxygenation of the feedstock to remove oxygen as well as
hydrogenation to saturate olefins. Cracking may also occur.
Decarboxylation, decarbonylation, and hydrodeoxygenation are herein
collectively referred to as deoxygenation reactions.

[0086]The full deoxygenation zone conditions include a relatively low
pressure of about 6890 kPa (1000 psia) to about 13,790 kPa (2000 psia), a
temperature of about 300° C. to about 500° C. and a liquid
hourly space velocity of about 0.1 to about 3 hr-1 based on fresh
feed not recycle. In another embodiment the deoxygenation conditions
include the same pressure of about 6890 kPa (1000 psia) to about 6895 kPa
(1700 psia), a temperature of about 350° C. to about 450°
C. and a liquid hourly space velocity of about 0.15 to about 0.40
hr-1. It is envisioned and is within the scope of this invention
that all the reactions are occurring simultaneously within a zone.

Example of Cyclic Rich Component

[0087]A whole mixed-wood pyrolysis oil feedstock was fed once-through a
fixed bed reactor loaded with a hydrotreating catalyst at the conditions
specified for partial deoxygenation zone (Zone 1) in Table 2 below. The
effluent oil was isolated after separation of water generated in the
reaction. The properties of the effluent oil from the partial
deoxygenation zone are also shown in Table 2. The partially deoxygenated
effluent oil from the partial deoxygenation zone was then fed to a full
deoxygenation zone and contacted with a second catalyst at the elevated
process conditions shown in Table 2. This second catalyst was a sulfided
nickel and molybdenum on alumina catalyst produced by UOP. The overall
volumetric yield of hydrocarbon that was isolated from the effluent of
the full deoxygenation zone was about 51 vol % of the initial whole
mixed-wood pyrolysis oil feedstock.

[0088]A whole pyrolysis oil feedstock produced from corn stover was fed
once-through a fixed bed reactor loaded with a hydrotreating catalyst at
the conditions specified for the partial deoxygenation zone (Zone 1) in
Table 3 below. The effluent oil was isolated after separation of water
generated in the reaction. The properties of the effluent oil from the
partial deoxygenation zone are also shown in Table 3. The partially
deoxygenated effluent from the partial deoxygenation zone was then fed
over a second catalyst in a full oxygenation zone at the elevated process
conditions shown. This second catalyst was a sulfided nickel molybdenum
on alumina catalyst produced by UOP. The overall volumetric yield of
hydrocarbon isolated from the effluent of the full deoxygenation zone was
about 67 vol % of the initial whole pyrolysis oil feedstock produced from
corn stover.

[0089]The third example again shows the complete deoxygenation of a whole
pyrolysis oil produced from corn stover. The pyrolysis oil was fed
once-through over a stacked fixed bed reactor. The upper zone of the
reactor, the partial deoxygenation zone, was loaded with a milder
hydrotreating catalyst run 250° C. as shown in Table 4. The bottom
zone of the reactor, the full deoxygenation zone, was loaded a sulfided
nickel and molybdenum on alumina catalyst produced by UOP and kept at
400° C. The other process variables are shown in Table 4. This
example shows that a single reactor with stacked catalyst beds is capable
of full deoxygenation to produce a hydrocarbon product.

[0090]Table 5 shows the typical distribution of hydrocarbon classes
produced after full deoxygenation of whole pyrolysis oil. The final
distribution depends on the feedstock processed, catalyst choice, and
process conditions. The distribution of the final product from example 2
above is shown in the "Example 2 Product" column. This represents a
hydrocarbon product produced from solid corn stover pyrolysis oil
processed as described in Table 3.

[0091]The boiling point distribution of several fully deoxygenated
pyrolysis oils is shown in FIG. 4. As shown the hydrocarbon product
produced has a wide boiling point range with significant fractions in the
range for each fuel. Some heavier components are also present that fall
outside the range of gasoline, aviation fuel, and diesel. These heavy
components could be recycled back into the second zone for further
hydrocracking or be isolated for other industrial uses.

Blending the Paraffin Rich Component and the Cyclic Rich Component

[0092]At least one paraffin rich component and at least one cyclic rich
component are blended to produce a target fuel. The target fuel may be in
the gasoline boiling point range, the diesel boiling point range, in the
aviation boiling point range, or multiple fuels may be produced in any
combination of the boiling point ranges. Other components or additives
may be incorporated into the blending so that the target fuel meets
additional specifications. Many fuels are defined by a set of physical
and chemical specifications. For a blend to be called a certain type of
fuel, it must meet the required specifications. If a first component does
not meet the desired specifications, one or more additional components
are blended with the first component so that the final blended product
meets the desired specifications. For example, the paraffin rich
component obtained above may not meet a particular specification of a
target fuel. Blending of the paraffin rich component with the cyclic
component would enable the blended fuel to meet at least some of the
specifications. The relative amounts of the components being blended is
determined by the specification to be met and the influence each
component has on the specification. As an example, the paraffin rich
component may not meet the density requirement for specific types of jet
fuel such as JP-8. But when blended with a cyclic rich component, the
blended fuel now meets the density requirements. Blending must be
conducted with accounting for all the specifications to be met. For
example, the blending of the paraffin rich component and the cyclic rich
component to meet the density requirements of JP-8, must also take into
consideration meeting the cloud point requirement, flash point
requirement, and other requirements for the target fuel. Models and
algorithms may be employed to assist in determine the relative amounts of
the components being blended.

[0093]A particular advantage of blending the paraffin rich component and
the cyclic rich component is that the resulting target fuel comprises at
least two components that were produced from renewable feedstocks. If the
target fuel can be produced through the blending of these two components,
then the target fuel would be wholly derived from renewable sources.
Another advantage of some embodiments of the invention is the opportunity
to produce the paraffin rich component and the cyclic rich component from
the same renewable source. For example, corn or soy beans may be
processed to produce vegetable oil which is the feedstock to the process
which produces the paraffin rich component. Biomass is a byproduct of the
corn or soy bean processing to produce vegetable oil. This biomass may be
pyrolized to generate the pyrolysis oil that is the feedstock to the
process which produces the cyclic rich component. Therefore, a single
renewable source, such as the corn or soybeans, provide the feedstocks to
both of the processes, one generating the paraffin rich component and one
generating the cyclic rich component. Corn and soybeans are merely
illustrative of the concept, and the single renewable source may be any
of those sources which provide the renewable feedstocks discussed above.

[0094]Another possible advantage includes integrating the process which
produces the paraffin rich component and the process which produces the
cyclic rich component. One point of integration is the product
fractionation zone. It is envisioned that the product fractionation zone
of the process to generate the paraffin rich component and the
fractionation zone of the process to generate the cyclic rich component
may be integrated. In this embodiment, the blending of the two components
occurs prior to the fractionation of the combined product streams.

[0095]Table 6 shows one example of a benefit of blending renewable-derived
feedstocks as described herein. Freeze point, flash point and density are
key specifications for aviation fuels. Line 2 of Table 6 shows that the
paraffin rich component produced by hydrodeoxygenation,
hydroisomerization and partial hydrocracking of soybean oil gives, upon
fractionation, a fuel product that meets aviation fuel specification for
freeze point and flash point but not for density (MTL-DTL-83133).
Similarly, hydrocarbon derived by hydrodeoxygenation of pyrolysis oil
from corn stover (Line 3 of Table 6) or wood (Line 4 of Table 6) do not
meet density specification. Blends of the soybean oil-derived paraffin
component with the cyclic rich component derived from pyrolysis oil,
however, do meet the density specification (Lines 5 and 6 of Table 6).
Specific blends are prepared according to the properties of the
individual components and the properties of the desired final hydrocarbon
fuel. Thus a clear benefit in fuel quality by blending renewable-derived
hydrocarbon components has been demonstrated.